EP4129265A1 - Gradient resin, preparation method therefor and use thereof - Google Patents
Gradient resin, preparation method therefor and use thereof Download PDFInfo
- Publication number
- EP4129265A1 EP4129265A1 EP20955929.3A EP20955929A EP4129265A1 EP 4129265 A1 EP4129265 A1 EP 4129265A1 EP 20955929 A EP20955929 A EP 20955929A EP 4129265 A1 EP4129265 A1 EP 4129265A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- poly
- layer
- resin
- methacrylate
- gradient
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000011347 resin Substances 0.000 title claims abstract description 90
- 229920005989 resin Polymers 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 84
- 230000007704 transition Effects 0.000 claims abstract description 43
- 239000000049 pigment Substances 0.000 claims abstract description 22
- 230000008859 change Effects 0.000 claims abstract description 18
- -1 poly(methyl methacrylate) Polymers 0.000 claims description 254
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 193
- 239000010410 layer Substances 0.000 claims description 167
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 150
- 239000004408 titanium dioxide Substances 0.000 claims description 96
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 91
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 91
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 91
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 91
- 235000012756 tartrazine Nutrition 0.000 claims description 74
- UJMBCXLDXJUMFB-GLCFPVLVSA-K tartrazine Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-GLCFPVLVSA-K 0.000 claims description 74
- 239000004149 tartrazine Substances 0.000 claims description 74
- 229960000943 tartrazine Drugs 0.000 claims description 74
- 238000000465 moulding Methods 0.000 claims description 52
- 239000000463 material Substances 0.000 claims description 40
- 229940051164 ferric oxide yellow Drugs 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- 239000004793 Polystyrene Substances 0.000 claims description 21
- 229920002223 polystyrene Polymers 0.000 claims description 21
- 239000003086 colorant Substances 0.000 claims description 15
- 238000003892 spreading Methods 0.000 claims description 15
- 230000007480 spreading Effects 0.000 claims description 15
- 239000011229 interlayer Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000013517 stratification Methods 0.000 claims description 11
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 229920006324 polyoxymethylene Polymers 0.000 claims description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- JSKUQVBNGZGWIN-UHFFFAOYSA-N [Ce].[Pr] Chemical compound [Ce].[Pr] JSKUQVBNGZGWIN-UHFFFAOYSA-N 0.000 claims description 2
- DIVGJYVPMOCBKD-UHFFFAOYSA-N [V].[Zr] Chemical compound [V].[Zr] DIVGJYVPMOCBKD-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 229920005593 poly(benzyl methacrylate) Polymers 0.000 claims description 2
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 claims description 2
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 claims description 2
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 claims description 2
- 229920000205 poly(isobutyl methacrylate) Polymers 0.000 claims description 2
- 229920000196 poly(lauryl methacrylate) Polymers 0.000 claims description 2
- 229920002776 polycyclohexyl methacrylate Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000129 polyhexylmethacrylate Polymers 0.000 claims description 2
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 96
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000008569 process Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000057 synthetic resin Substances 0.000 description 6
- 229920003002 synthetic resin Polymers 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000004851 dental resin Substances 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007676 flexural strength test Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- A61K6/889—Polycarboxylate cements; Glass ionomer cements
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/78—Pigments
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- A61K6/893—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/04—Conditioning or physical treatment of the material to be shaped by cooling
- B29B13/045—Conditioning or physical treatment of the material to be shaped by cooling of powders or pellets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/06—Conditioning or physical treatment of the material to be shaped by drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/58—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/58—Measuring, controlling or regulating
- B29C2043/5808—Measuring, controlling or regulating pressure or compressing force
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/58—Measuring, controlling or regulating
- B29C2043/5816—Measuring, controlling or regulating temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/25—Solid
- B29K2105/251—Particles, powder or granules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
- B29K2995/002—Coloured
- B29K2995/0021—Multi-coloured
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/753—Medical equipment; Accessories therefor
- B29L2031/7532—Artificial members, protheses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/753—Medical equipment; Accessories therefor
- B29L2031/7532—Artificial members, protheses
- B29L2031/7536—Artificial teeth
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2359/00—Characterised by the use of polyacetals containing polyoxymethylene sequences only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2289—Oxides; Hydroxides of metals of cobalt
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
Definitions
- the present application belongs to the technical field of gradient resins, and relates to a gradient resin, a preparation method therefor and use thereof, for example, a gradient aesthetic dental resin material, a preparation method therefor and use thereof, and in particular, a natural-transition gradient aesthetic dental resin material, a preparation method therefor and use thereof.
- the CAD/CAM gradient dental PMMA resin is suitable for temporary restorations: single crown, bridge, full mouth reconstruction, etc., and has the advantages of high glossiness and good luminous transmittance, but the existing process is mostly to prepare semi-solid sheets with different colors firstly, and then stack all the sheets in the mold according to the color order for a hot-press molding, and the products produced by this molding process generally have obvious interlayer boundaries and unnatural color transitions.
- CN103273713B discloses a four-layer-color synthetic resin block and a preparation method therefor.
- the four-layer-color synthetic resin block is sequentially composed of structures of four layers, and the structure of each layer includes compositions as follows: poly(methyl methacrylate), iron oxide red, iron oxide black, iron oxide yellow, titanium white, methyl methacrylate and ethylene glycol dimethacrylate.
- the preparation method includes the steps as follows: a poly(methyl methacrylate) powder is dried at a temperature of 80-90°C; materials used for the four layers are prepared in proportion respectively, and the material used for each layer is required to be mixed uniformly and kneaded until a dough stage, so that a plastic dough material is formed; four layers of the plastic dough materials are subjected to a hot-press molding and bonded together in sequence in a mold, a hot-press temperature is 110-130°C, and a hot-press time is 10-20 min; the four-layer-color synthetic resin block after hot-press molding is subjected to a heat treatment at a temperature of 80-90°C for 10-12 h, so as to obtain the four-layer-color synthetic resin block product.
- a dental model or temporary crown bridge, which is processed through this invention, is natural and vivid in color.
- poly(methyl methacrylate), methyl methacrylate and ethylene glycol dimethacrylate were used to prepare the materials used for the four layers respectively, mixed uniformly, kneaded to the dough stage, and then subjected to the hot-press molding in sequence to obtain the four-layer-color synthetic resin block.
- such four-layer-color resin has the problems of serious layer stratification and unnatural color transition, which affect the use effect during use.
- CN108078789A discloses a preparation method for a multi-color integrated dental restoration material, relates to the technical field of false tooth restoration materials, and solves the problem that the restoration layer of the existing multi-color restoration material is easily separated during processing.
- the method includes the following steps: one, various compositions are added to multiple containers, the temperature is controlled at 10-25°C, and the compositions are stirred for 3-5 min, mixed uniformly and then allowed to stand for 10-20 min, so that the mixtures are turned into a thick gel form, and the mixtures with different colors are obtained; two, the mixtures with different colors are placed in an environment at less than or equal to -15°C for cooling, so as to obtain semi-cured mixtures with different colors; three, multiple semi-cured mixtures with different colors are taken out and stacked in a mold with openings at the two ends, the mold is sealed by moving an upper mold and a lower mold towards each other, and the mixtures are heated to 40-80°C, pressure-polymerized, cured-molded, and removed from the mold
- the gradient-color dental restoration material prepared by this invention is high in interface strength and material consistency, good in impact resistance and high in manufacturing precision.
- poly(methyl methacrylate), methyl methacrylate, a curing agent and a pigment are mixed and stirred at a certain temperature to form the thick gel form mixture with different colors, and then cooled at -15°C to form the semi-cured mixture with different colors, and the semi-cured mixture is pressure-polymerized to obtain the multi-color integrated dental restoration material.
- the patent uses a two-step polymerization method to prepare dental restoration materials, which can precisely control the shape, thickness and color of the contact interface between adjacent layers, but the product boundary of this patent is still obvious, and the interlayer transition is unnatural.
- the common method in the prior art is to knead the different layers to the dough stage, and then subject the four layers of the plastic dough materials to a hot-press molding at 110°C -130°C and bond them together in sequence in a mold to obtain the four-layer-color synthetic resin block.
- the resin monomers are frozen at -15°C -0°C for more than or equal to 4 hours to obtain the gel-form materials, and the gel-form materials are poured into the mold according to the order of color shade separately, allowed to stand for more than or equal to 12 h at room temperature, and cured to obtain the dental restoration material.
- the gradient resins obtained by the above methods both have unnatural interlayer transition, the teeth can be found to be a layer stratification state under the sunlight, and the boundary line can be clearly seen, resulting in poor aesthetic effect of the cut teeth.
- the present application is to provide a gradient resin, a preparation method therefor and use thereof.
- the gradient resin prepared in the present application has natural color, the layers merge into each other, no transition boundary can be found between layers, and the performances of luminous transmittance and flexural strength are excellent.
- a first object of the present application is to provide a gradient resin, and in order to achieve this object, the present application adopts the technical solutions below.
- a gradient resin is provided, and the gradient resin is formed by merging different layers with color transition change, in which the color transition change range between two adjacent layers is 0.1-20%, and by mass percentage, the gradient resin is composed of 98-99.99% of a resin powder and 0.01-2% of a pigment.
- the color transition change between two adjacent layers refers to a mass content change of the pigment in the gradient resin raw materials of two adjacent layers.
- the gradient resin of the present application is prepared by mixing and hot-pressing the resin powder and the pigment without adding with any monomer or crosslinking agent; since the resin prepared by this method can be merged well between layers and has gentle interlayer color transition, the resin product has no layer stratification, and the color transition is natural.
- the color transition change may be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%, etc.; optionally, when the interlayer color transition is less than 7%, the product obtains the best color transition effect.
- the mass percentage of the resin powder may be 98%, 98.1%, 98.2%, 98.3%, 98.4%, 98.5%, 98.6%, 98.7%, 98.8%, 98.9%, 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, 99.99%, etc.
- the mass percentage of the pigment may be 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2%, etc.
- a particle size of the resin powder is 0.1-200 ⁇ m, such as 0.1 ⁇ m, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 20 ⁇ m, 30 ⁇ m, 40 ⁇ m, 50 ⁇ m, 60 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m, 100 ⁇ m, 110 ⁇ m, 120 ⁇ m, 130 ⁇ m, 140 ⁇ m, 150 ⁇ m, 160 ⁇ m, 170 ⁇ m, 180 ⁇ m, 190 ⁇ m or 200 ⁇ m, etc; the particle size is optionally 30-150 ⁇ m, more optionally 40-100 ⁇ m.
- a molecular mass of the resin powder is 100000-1000000, such as 100000, 200000, 300000, 400000, 500000, 600000, 700000, 800000, 900000 or 1000000, etc; the molecular mass is optionally 300000-700000, more optionally 400000-600000.
- the resin powder includes any one or a mixture of at least two of poly(methyl methacrylate), poly(ethyl methacrylate), poly(propyl methacrylate), poly(n-butyl methacrylate), poly(isobutyl methacrylate), poly(hexyl methacrylate), poly(dicyclopentenyl methacrylate), poly(tetrahydrofurfuryl methacrylate), poly(2-hydroxyethyl methacrylate), poly(glycidyl methacrylate), poly(lauryl methacrylate), poly(cyclohexyl methacrylate), poly(benzyl methacrylate), poly(allyl methacrylate), poly(2-ethoxyethyl methacrylate), methoxy polyethylene glycol methacrylate, poly(glycerol methacrylate), poly(isobornyl methacrylate), polyvinyl chloride, polystyrene, polyoxymethylene, polyacetaldehyde and poly
- the pigment includes any one or a mixture of at least two of zirconium vanadium yellow, cerium praseodymium yellow, tartrazine, ferric oxide yellow, chrome yellow, sunset red, iron oxide red, erbium oxide, titanium dioxide, cobalt oxide, chromium oxide, iron oxide brown, iron oxide black and carbon black.
- a second object of the present application is to provide a preparation method for the gradient resin according to the first object, including the following steps:
- step 2) the color transition change range between two adjacent layers is 0.1-20%.
- a temperature of the hot-press molding is 60-220°C; for example, the temperature of the hot-press molding is 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, or 220°C, etc., optionally 100-180°C, more optionally 120-160°C.
- a pressure of the hot-press molding is 1-20 MPa; for example, the pressure of the hot-press molding is 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, 11 MPa, 12 MPa, 13 MPa, 14 MPa, 15 MPa, 16 MPa, 17 MPa, 18 MPa, 19 MPa, 20 MPa, etc., optionally 4-15 MPa, and more optionally 8-12 MPa.
- the preparation method further includes a pretreatment step for the resin powder before step 1);
- the pretreatment includes drying, and a temperature of the drying is 80-100°C; for example, the temperature of the drying is 80°C, 85°C, 90°C, 95°C, or 100°C, etc.; a time of the drying is 1-3 h; for example, the time of the drying is 1 h, 1.5 h, 2 h, 2.5 h, or 3 h, etc.
- a preparation method for the gradient resin includes the following steps:
- a third object of the present application is to use of the gradient resin according to the first object, in which the gradient resin is used in preparing a gradient dental restoration, and the aesthetic effect of the teeth is excellent.
- the gradient resin of the present application has a simple preparation method; the gradient resin is prepared by mixing and hot-pressing the resin powder and the pigment without adding with any monomer or crosslinking agent; since the resin prepared by this method can be merged well between layers and has gentle interlayer color transition, the prepared gradient resin product has no layer stratification, the color transition is natural, the layers merge into each other, no transition boundary can be found between layers, the interlayer color transition change range is 0.1-20%, and it is invisible to the naked eye; the prepared gradient resin has a luminous transmittance of more than or equal to 50%, a flexural strength of more than 100 MPa, a Vickers hardness of more than 20 HV, a water absorption value of less than 25 ⁇ g/cm 3 , and a solubility value of less than 5 ⁇ g/cm 3 .
- the gradient resin prepared in the present application has excellent aesthetic effect when used in dental materials.
- a preparation method for the gradient resin of this example includes the following steps:
- poly(methyl methacrylate) had a particle size of 40 ⁇ m and a molecular mass of 500000.
- a preparation method for the gradient resin of this example includes the following steps:
- the polystyrene powder had a particle size of 45 ⁇ m and a molecular mass of 400000.
- a preparation method for the gradient resin of this example includes the following steps:
- the polyoxymethylene resin had a particle size of 60 ⁇ m and a molecular mass of 550000.
- Example 2 differs from Example 1 in that the particle size of poly(methyl methacrylate) was 0.05 ⁇ m, and the others were the same as those of Example 1.
- Example 2 differs from Example 1 in that the particle size of poly(methyl methacrylate) was 300 ⁇ m, and the others were the same as those of Example 1.
- Example 1 differs from Example 1 in that the molecular mass of poly(methyl methacrylate) was 50000, and the others were the same as those of Example 1.
- Example 1 differs from Example 1 in that the molecular mass of poly(methyl methacrylate) was 1500000, and the others were the same as those of Example 1.
- Example 2 differs from Example 1 in that the resin powder is a polyether ether ketone powder, and the others were the same as those of Example 1.
- This comparative example differs from Example 1 in that the mass percentage of the resin powder was 90%, and the mass percentage of the pigment was 10%, and the specific composition is as follows:
- This comparative example differs from Example 1 in that the mass percentage of the resin powder was 99.9994%, and the mass percentage of the pigment was 0.0006%, and the specific composition is as follows:
- test standard of luminous transmittance refers to GB2410-2008, and the test method is as follows: a sample with a size of 30 mm ⁇ 30 mm ⁇ 1 mm was prepared, and tested by a haze meter.
- the test standard of flexural strength refers to ISO 10477-2018, and the test method is as follows: Three-point flexural test: 5 strength bars of (2 ⁇ 0.1 mm) ⁇ (2 ⁇ 0.1 mm) ⁇ (25 ⁇ 1 mm) were cut for the flexural strength test. The inspector put the strength bar on an electric tensile testing apparatus for testing, and the spacing was 20 mm; the load was applied at a loading rate of 1 ⁇ 0.1 mm/min until the sample fractured; the 5 samples were tested respectively, and the strength value of each sample was recorded, and taken the average value.
- test standard of Vickers hardness refers to GB/T4340.1-2009, and the test method is as follows: Three-point test: the finished product piece was placed on a Vickers hardness tester for testing, and hardness values at three different positions were measured and taken the average value.
- Water absorption value and solubility value refers to ISO 10477-2018, and the test method is as follows: 5 test round pieces with a size of ⁇ 15 ⁇ 1 mm ⁇ (1.0 ⁇ 0.2) mm were prepared. 2000-grit sandpaper was used for water polishing, and a caliper was used to measure the diameter and thickness of the samples to an accuracy of 0.01 mm. The sample volume was calculated and expressed in mm 3 .
- ⁇ s 1 m 1 ⁇ m 3 / V in the formula: m 1 - the constant mass of the sample before being soaked in water with a unit of micrograms ( ⁇ g); m 3 - the constant mass of the sample after being soaked in water for 7d with a unit of micrograms ( ⁇ g); V - the sample volume with a unit of cubic millimeters (mm 3 ).
- the gradient resin product obtained in the present application has no layer stratification; the color transition is natural, the layers merge into each other, no transition boundary can be found between layers, the interlayer color transition change range is 0.1%-20%, and it is invisible to the naked eye; the prepared gradient resin has a luminous transmittance of 55-65%, a flexural strength of more than 100 MPa, a Vickers hardness of more than 20 HV, a water absorption value of less than 25 ⁇ g/cm 3 , and a solubility value of less than 5 ⁇ g/cm 3 .
- the particle size of poly(methyl methacrylate) is too large in Example 5, resulting in that the pigment will be prevented from entering the powder inside, and the prepared disc will have non-uniform color.
- the molecular mass of poly(methyl methacrylate) is too small in Example 6, resulting in that the overall molecular mass of the product obtained from press molding will be too low, and the polymer with low molecular mass will be too much, which can be easily dissolved in the mouth.
- the molecular mass of poly(methyl methacrylate) is too large in Example 7, resulting in that the raw material cannot be melted and press-molded due to the excessively high hardness.
- the resin powder is replaced with polyether ether ketone in Example 8, resulting in that the melting and pressing cannot be achieved with the same process.
- the mass percentage of the resin powder is too small in Comparative Example 3, resulting in that the pigment content will be too high, the color will be too dark, and the tooth color consistent with the color guide cannot be customized.
- the mass percentage of the resin powder is too large in Comparative Example 4, resulting in that the pigment content will be low, the color will be too light, and the tooth color consistent with the color guide cannot be customized.
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Abstract
Description
- The present application belongs to the technical field of gradient resins, and relates to a gradient resin, a preparation method therefor and use thereof, for example, a gradient aesthetic dental resin material, a preparation method therefor and use thereof, and in particular, a natural-transition gradient aesthetic dental resin material, a preparation method therefor and use thereof.
- Currently, with the improvement of people's living standards and the progress of science and technology, there are increasing requirements for dental aesthetic restoration, which thus give a rise to the requirements for multi-layer gradient resin. The CAD/CAM gradient dental PMMA resin is suitable for temporary restorations: single crown, bridge, full mouth reconstruction, etc., and has the advantages of high glossiness and good luminous transmittance, but the existing process is mostly to prepare semi-solid sheets with different colors firstly, and then stack all the sheets in the mold according to the color order for a hot-press molding, and the products produced by this molding process generally have obvious interlayer boundaries and unnatural color transitions.
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CN103273713B discloses a four-layer-color synthetic resin block and a preparation method therefor. The four-layer-color synthetic resin block is sequentially composed of structures of four layers, and the structure of each layer includes compositions as follows: poly(methyl methacrylate), iron oxide red, iron oxide black, iron oxide yellow, titanium white, methyl methacrylate and ethylene glycol dimethacrylate. The preparation method includes the steps as follows: a poly(methyl methacrylate) powder is dried at a temperature of 80-90°C; materials used for the four layers are prepared in proportion respectively, and the material used for each layer is required to be mixed uniformly and kneaded until a dough stage, so that a plastic dough material is formed; four layers of the plastic dough materials are subjected to a hot-press molding and bonded together in sequence in a mold, a hot-press temperature is 110-130°C, and a hot-press time is 10-20 min; the four-layer-color synthetic resin block after hot-press molding is subjected to a heat treatment at a temperature of 80-90°C for 10-12 h, so as to obtain the four-layer-color synthetic resin block product. A dental model or temporary crown bridge, which is processed through this invention, is natural and vivid in color. In this patent, poly(methyl methacrylate), methyl methacrylate and ethylene glycol dimethacrylate were used to prepare the materials used for the four layers respectively, mixed uniformly, kneaded to the dough stage, and then subjected to the hot-press molding in sequence to obtain the four-layer-color synthetic resin block. However, such four-layer-color resin has the problems of serious layer stratification and unnatural color transition, which affect the use effect during use. -
CN108078789A discloses a preparation method for a multi-color integrated dental restoration material, relates to the technical field of false tooth restoration materials, and solves the problem that the restoration layer of the existing multi-color restoration material is easily separated during processing. The method includes the following steps: one, various compositions are added to multiple containers, the temperature is controlled at 10-25°C, and the compositions are stirred for 3-5 min, mixed uniformly and then allowed to stand for 10-20 min, so that the mixtures are turned into a thick gel form, and the mixtures with different colors are obtained; two, the mixtures with different colors are placed in an environment at less than or equal to -15°C for cooling, so as to obtain semi-cured mixtures with different colors; three, multiple semi-cured mixtures with different colors are taken out and stacked in a mold with openings at the two ends, the mold is sealed by moving an upper mold and a lower mold towards each other, and the mixtures are heated to 40-80°C, pressure-polymerized, cured-molded, and removed from the mold to obtain the multi-color integrated dental restoration material. The gradient-color dental restoration material prepared by this invention is high in interface strength and material consistency, good in impact resistance and high in manufacturing precision. In this patent, poly(methyl methacrylate), methyl methacrylate, a curing agent and a pigment are mixed and stirred at a certain temperature to form the thick gel form mixture with different colors, and then cooled at -15°C to form the semi-cured mixture with different colors, and the semi-cured mixture is pressure-polymerized to obtain the multi-color integrated dental restoration material. The patent uses a two-step polymerization method to prepare dental restoration materials, which can precisely control the shape, thickness and color of the contact interface between adjacent layers, but the product boundary of this patent is still obvious, and the interlayer transition is unnatural. - The common method in the prior art is to knead the different layers to the dough stage, and then subject the four layers of the plastic dough materials to a hot-press molding at 110°C -130°C and bond them together in sequence in a mold to obtain the four-layer-color synthetic resin block. Or the resin monomers are frozen at -15°C -0°C for more than or equal to 4 hours to obtain the gel-form materials, and the gel-form materials are poured into the mold according to the order of color shade separately, allowed to stand for more than or equal to 12 h at room temperature, and cured to obtain the dental restoration material. The gradient resins obtained by the above methods both have unnatural interlayer transition, the teeth can be found to be a layer stratification state under the sunlight, and the boundary line can be clearly seen, resulting in poor aesthetic effect of the cut teeth.
- At present, it is difficult for multi-layer gradient resin materials to achieve natural interlayer transition without stratification. Therefore, it is necessary to develop a novel multi-layer gradient resin material with natural interlayer transition without stratification.
- The present application is to provide a gradient resin, a preparation method therefor and use thereof. The gradient resin prepared in the present application has natural color, the layers merge into each other, no transition boundary can be found between layers, and the performances of luminous transmittance and flexural strength are excellent.
- A first object of the present application is to provide a gradient resin, and in order to achieve this object, the present application adopts the technical solutions below.
- A gradient resin is provided, and the gradient resin is formed by merging different layers with color transition change, in which the color transition change range between two adjacent layers is 0.1-20%, and by mass percentage, the gradient resin is composed of 98-99.99% of a resin powder and 0.01-2% of a pigment.
- It should be noted that the color transition change between two adjacent layers refers to a mass content change of the pigment in the gradient resin raw materials of two adjacent layers.
- The gradient resin of the present application is prepared by mixing and hot-pressing the resin powder and the pigment without adding with any monomer or crosslinking agent; since the resin prepared by this method can be merged well between layers and has gentle interlayer color transition, the resin product has no layer stratification, and the color transition is natural.
- It is found in the present application by analyzing the layer stratification and transition that, when the interlayer color transition is less than 20%, the product exhibits a good color transition effect, and no interlayer boundary can be seen. The color transition change may be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%, etc.; optionally, when the interlayer color transition is less than 7%, the product obtains the best color transition effect. By mass percentage, the mass percentage of the resin powder may be 98%, 98.1%, 98.2%, 98.3%, 98.4%, 98.5%, 98.6%, 98.7%, 98.8%, 98.9%, 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, 99.99%, etc., and the mass percentage of the pigment may be 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2%, etc.
- A particle size of the resin powder is 0.1-200 µm, such as 0.1 µm, 0.5 µm, 1 µm, 2 µm, 3 µm, 4 µm, 5 µm, 6 µm, 7 µm, 8 µm, 9 µm, 10 µm, 20 µm, 30 µm, 40 µm, 50 µm, 60 µm, 70 µm, 80 µm, 90 µm, 100 µm, 110 µm, 120 µm, 130 µm, 140 µm, 150 µm, 160 µm, 170 µm, 180 µm, 190 µm or 200 µm, etc; the particle size is optionally 30-150 µm, more optionally 40-100 µm.
- A molecular mass of the resin powder is 100000-1000000, such as 100000, 200000, 300000, 400000, 500000, 600000, 700000, 800000, 900000 or 1000000, etc; the molecular mass is optionally 300000-700000, more optionally 400000-600000.
- The resin powder includes any one or a mixture of at least two of poly(methyl methacrylate), poly(ethyl methacrylate), poly(propyl methacrylate), poly(n-butyl methacrylate), poly(isobutyl methacrylate), poly(hexyl methacrylate), poly(dicyclopentenyl methacrylate), poly(tetrahydrofurfuryl methacrylate), poly(2-hydroxyethyl methacrylate), poly(glycidyl methacrylate), poly(lauryl methacrylate), poly(cyclohexyl methacrylate), poly(benzyl methacrylate), poly(allyl methacrylate), poly(2-ethoxyethyl methacrylate), methoxy polyethylene glycol methacrylate, poly(glycerol methacrylate), poly(isobornyl methacrylate), polyvinyl chloride, polystyrene, polyoxymethylene, polyacetaldehyde and polyurethane.
- The pigment includes any one or a mixture of at least two of zirconium vanadium yellow, cerium praseodymium yellow, tartrazine, ferric oxide yellow, chrome yellow, sunset red, iron oxide red, erbium oxide, titanium dioxide, cobalt oxide, chromium oxide, iron oxide brown, iron oxide black and carbon black.
- A second object of the present application is to provide a preparation method for the gradient resin according to the first object, including the following steps:
- 1) preparing colored powders: weighing and uniformly mixing the pigment and the resin powder for preparing colored powders with different colors according to respective color formulas, and weighing and proportioning the colored powders for each layer according to a layer configuration;
- 2) spreading the materials: adding the colored powders with different colors obtained in step 1) into a molding mold in sequence, spreading one colored powder flat out in the molding mold, then adding another colored powder of the next layer and spreading the colored powder flat out until all the colored powders have been added; and
- 3) performing a press molding: subjecting the mold to a hot-press molding, and taking the mold out after cooling, so as to obtain the gradient resin.
- In step 2), the color transition change range between two adjacent layers is 0.1-20%.
- Optionally, in step 3), a temperature of the hot-press molding is 60-220°C; for example, the temperature of the hot-press molding is 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, or 220°C, etc., optionally 100-180°C, more optionally 120-160°C.
- Optionally, in step 3), a pressure of the hot-press molding is 1-20 MPa; for example, the pressure of the hot-press molding is 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, 11 MPa, 12 MPa, 13 MPa, 14 MPa, 15 MPa, 16 MPa, 17 MPa, 18 MPa, 19 MPa, 20 MPa, etc., optionally 4-15 MPa, and more optionally 8-12 MPa.
- Optionally, the preparation method further includes a pretreatment step for the resin powder before step 1);
Optionally, the pretreatment includes drying, and a temperature of the drying is 80-100°C; for example, the temperature of the drying is 80°C, 85°C, 90°C, 95°C, or 100°C, etc.; a time of the drying is 1-3 h; for example, the time of the drying is 1 h, 1.5 h, 2 h, 2.5 h, or 3 h, etc. - As an optional solution of the present application, a preparation method for the gradient resin includes the following steps:
- 1) preparing colored powders: drying the resin powder at 80-100°C for 1-3 h, weighing and uniformly mixing the pigment and the resin powder for preparing colored powders with different colors according to respective color formulas, and weighing and proportioning the colored powders for each layer according to a layer configuration;
- 2) spreading the materials: adding the colored powders with different colors obtained in step 1) into a molding mold in sequence, spreading one colored powder flat out in the molding mold, then adding another colored powder of the next layer and spreading the colored powder flat out until all the colored powders have been added, in which the color transition change range between two adjacent layers is 0.1-20%; and
- 3) performing a press molding: subjecting the materials to be molded to a hot-press molding in the mold, and removing the mold after molding, so as to obtain the gradient resin with natural interlayer transition and no color stratification, in which an optional press method is a hot-press molding, and the mold is removed after cooling, a temperature of the hot-press molding is 60-220°C, and a pressure of the hot-press molding is 1-20 MPa.
- A third object of the present application is to use of the gradient resin according to the first object, in which the gradient resin is used in preparing a gradient dental restoration, and the aesthetic effect of the teeth is excellent.
- Compared with the prior art, the beneficial effects of the present application are as follows.
- The gradient resin of the present application has a simple preparation method; the gradient resin is prepared by mixing and hot-pressing the resin powder and the pigment without adding with any monomer or crosslinking agent; since the resin prepared by this method can be merged well between layers and has gentle interlayer color transition, the prepared gradient resin product has no layer stratification, the color transition is natural, the layers merge into each other, no transition boundary can be found between layers, the interlayer color transition change range is 0.1-20%, and it is invisible to the naked eye; the prepared gradient resin has a luminous transmittance of more than or equal to 50%, a flexural strength of more than 100 MPa, a Vickers hardness of more than 20 HV, a water absorption value of less than 25 µg/cm3, and a solubility value of less than 5 µg/cm3. The gradient resin prepared in the present application has excellent aesthetic effect when used in dental materials.
- The technical solutions of the present application are further described below through specific embodiments.
- Unless otherwise specified, various raw materials of the present application can be purchased commercially or prepared according to conventional methods in the art.
- A preparation method for the gradient resin of this example includes the following steps:
- (1) raw material drying: a poly(methyl methacrylate) powder was dried at 90°C for 2 h;
- (2) colored powders preparation: the pigment and the poly(methyl methacrylate) powder were mixed uniformly according to color formulas, and each layer was required to have a uniform color without material spots, in which a color transition difference of each layer was 5%;
- (3) spreading the colored powders: the colored powder of the first layer was added into a molding mold and spread flat out, and the materials were spread layer by layer until all the colored powders have been spread; and
- (4) press molding: press molding was performed without exceeding the pressure that the materials were able to withstand, a temperature of a hot-press molding was 150°C, and a time was 60 min. After the hot-press molding, the materials were cooled to room temperature under the same pressure.
- In the method, mass percentages of each composition of the materials are described below separately:
- the first layer: poly(methyl methacrylate): 99.9354%, iron oxide red: 0.00131%, tartrazine: 0.01414%, titanium dioxide: 0.04687%, cobalt oxide: 0.00232%;
- the second layer: poly(methyl methacrylate): 99.9386%, iron oxide red: 0.00124%, tartrazine: 0.01343%, titanium dioxide: 0.04453%, cobalt oxide: 0.00220%;
- the third layer: poly(methyl methacrylate): 99.9418%, iron oxide red: 0.00117%, tartrazine: 0.01273%, titanium dioxide: 0.04218%, cobalt oxide: 0.00209%;
- the fourth layer: poly(methyl methacrylate): 99.9451%, iron oxide red: 0.00111%, tartrazine: 0.01202%, titanium dioxide: 0.03984%, cobalt oxide: 0.00197%;
- the fifth layer: poly(methyl methacrylate): 99.9483%, iron oxide red: 0.00104%, tartrazine: 0.01131%, titanium dioxide: 0.03750%, cobalt oxide: 0.00186%;
- the sixth layer: poly(methyl methacrylate): 99.9515%, iron oxide red: 0.00098%, tartrazine: 0.01061%, titanium dioxide: 0.03515%, cobalt oxide: 0.00174%;
- the seventh layer: poly(methyl methacrylate): 99.9548%, iron oxide red: 0.00091%, tartrazine: 0.00990%, titanium dioxide: 0.03281%, cobalt oxide: 0.00162%;
- the eighth layer: poly(methyl methacrylate): 99.9580%, iron oxide red: 0.00085%, tartrazine: 0.00919%, titanium dioxide: 0.03047%, cobalt oxide: 0.00151%;
- the ninth layer: poly(methyl methacrylate): 99.9612%, iron oxide red: 0.00078%, tartrazine: 0.00848%, titanium dioxide: 0.02812%, cobalt oxide: 0.00139%;
- the tenth layer: poly(methyl methacrylate): 99.9644%, iron oxide red: 0.00072%, tartrazine: 0.00778%, titanium dioxide: 0.02578%, cobalt oxide: 0.00128%;
- the eleventh layer: poly(methyl methacrylate): 99.9677%, iron oxide red: 0.00065%, tartrazine: 0.00707%, titanium dioxide: 0.02344%, cobalt oxide: 0.00116%;
- the twelfth layer: poly(methyl methacrylate): 99.9709%, iron oxide red: 0.000585%, tartrazine: 0.00636%, titanium dioxide: 0.02109%, cobalt oxide: 0.00104%;
- the thirteenth layer: poly(methyl methacrylate): 99.9741%, iron oxide red: 0.00052%, tartrazine: 0.00566%, titanium dioxide: 0.01875%, cobalt oxide: 0.00093%;
- the fourteenth layer: poly(methyl methacrylate): 99.9774%, iron oxide red: 0.00046%, tartrazine: 0.00495%, titanium dioxide: 0.01640%, cobalt oxide: 0.00081%;
- the fifteenth layer: poly(methyl methacrylate): 99.9806%, iron oxide red: 0.00039%, tartrazine: 0.00424%, titanium dioxide: 0.01406%, cobalt oxide: 0.00070%;
- the sixteenth layer: poly(methyl methacrylate): 99.9838%, iron oxide red: 0.00033%, tartrazine: 0.00354%, titanium dioxide: 0.01172%, cobalt oxide: 0.00058%;
- the seventeenth layer: poly(methyl methacrylate): 99.9871%, iron oxide red: 0.00026%, tartrazine: 0.00283%, titanium dioxide: 0.00937%, cobalt oxide: 0.00046%.
- In the method, poly(methyl methacrylate) had a particle size of 40 µm and a molecular mass of 500000.
- A preparation method for the gradient resin of this example includes the following steps:
- (1) raw material drying: a polystyrene powder was dried at 90°C for 2 h;
- (2) colored powders preparation: the pigment and the poly(methyl methacrylate) powder were mixed uniformly according to color formulas, and each layer was required to have a uniform color without material spots, in which a color transition difference of each layer was 6%;
- (3) spreading the colored powders: the colored powder of the first layer was added into a molding mold and spread flat out, and the colored powders were added layer by layer until all the colored powders have been spread; and
- (4) press molding: press molding was performed without exceeding the pressure that the materials were able to withstand, a temperature of a hot-press molding was 160°C, and a time was 50 min. After the hot-press molding, the materials were cooled to room temperature under the same pressure.
- In the method, mass percentages of each composition of the materials are described below separately:
- the first layer: polystyrene: 99.9402%, iron oxide red: 0.00120%, ferric oxide yellow: 0.01352%, titanium dioxide: 0.04293%, cobalt oxide: 0.00214%;
- the second layer: polystyrene: 99.9438%, iron oxide red: 0.00113%, ferric oxide yellow: 0.01271%, titanium dioxide: 0.04293%, cobalt oxide: 0.00214%;
- the third layer: polystyrene: 99.9474%, iron oxide red: 0.00106%, ferric oxide yellow: 0.01190%, titanium dioxide: 0.03778%, cobalt oxide: 0.00188%;
- the fourth layer: polystyrene: 99.9510%, iron oxide red: 0.00098%, ferric oxide yellow: 0.01109%, titanium dioxide: 0.03520%, cobalt oxide: 0.00175%;
- the fifth layer: polystyrene: 99.9546%, iron oxide red: 0.00091%, ferric oxide yellow: 0.01028%, titanium dioxide: 0.03263%, cobalt oxide: 0.00163%;
- the sixth layer: polystyrene: 99.9581%, iron oxide red: 0.00084%, ferric oxide yellow: 0.00946%, titanium dioxide: 0.03005%, cobalt oxide: 0.00150%;
- the seventh layer: polystyrene: 99.9617%, iron oxide red: 0.00077%, ferric oxide yellow: 0.00865%, titanium dioxide: 0.02748%, cobalt oxide: 0.00137%;
- the eighth layer: polystyrene: 99.9653%, iron oxide red: 0.00070%, ferric oxide yellow: 0.00784%, titanium dioxide: 0.02490%, cobalt oxide: 0.00124%;
- the ninth layer: polystyrene: 99.9689%, iron oxide red: 0.00062%, ferric oxide yellow: 0.00703%, titanium dioxide: 0.02232%, cobalt oxide: 0.00111%;
- the tenth layer: polystyrene: 99.9713%, iron oxide red: 0.00058%, ferric oxide yellow: 0.00649%, titanium dioxide: 0.02061%, cobalt oxide: 0.00103%;
- the eleventh layer: polystyrene: 99.9749%, iron oxide red: 0.00050%, ferric oxide yellow: 0.00568%, titanium dioxide: 0.01803%, cobalt oxide: 0.00090%;
- the twelfth layer: polystyrene: 99.9785%, iron oxide red: 0.00043%, ferric oxide yellow: 0.00487%, titanium dioxide: 0.01545%, cobalt oxide: 0.00070%;
- the thirteenth layer: polystyrene: 99.9821%, iron oxide red: 0.00036%, ferric oxide yellow: 0.00406%, titanium dioxide: 0.01288%, cobalt oxide: 0.00064%;
- the fourteenth layer: polystyrene: 99.9857%, iron oxide red: 0.00029%, ferric oxide yellow: 0.00324%, titanium dioxide: 0.01030%, cobalt oxide: 0.00051%;
- the fifteenth layer: polystyrene: 99.9892%, iron oxide red: 0.00022%, ferric oxide yellow: 0.00243%, titanium dioxide: 0.00773%, cobalt oxide: 0.00039%;
- the sixteenth layer: polystyrene: 99.9928%, iron oxide red: 0.00014%, ferric oxide yellow: 0.00162%, titanium dioxide: 0.00515%, cobalt oxide: 0.00026%;
- the seventeenth layer: polystyrene: 99.9964%, iron oxide red: 0.00007%, ferric oxide yellow: 0.00081%, titanium dioxide: 0.00258%, cobalt oxide: 0.00013%.
- In the method, the polystyrene powder had a particle size of 45 µm and a molecular mass of 400000.
- A preparation method for the gradient resin of this example includes the following steps:
- (1) raw material drying: a polyoxymethylene resin powder was dried at 90°C for 4 h;
- (2) colored powders preparation: the pigment and the polyoxymethylene resin powder were mixed uniformly according to color formulas, and each layer was required to have a uniform color without material spots, in which a color transition difference of each layer was 20%;
- (3) spreading the colored powders: the colored powder of the first layer was added into a molding mold and spread flat out, and the colored powders were spread layer by layer until all the colored powders for 17 layers have been spread; and
- (4) press molding: press molding was performed without exceeding the pressure that the materials were able to withstand, a temperature of a hot-press molding was 160°C, and a time was 50 min. After the hot-press molding, the materials were cooled to room temperature under the same pressure.
- In the method, mass percentages of each composition of the materials for each layer are described below separately:
- the first layer: polyoxymethylene resin: 99.5825%, sunset red: 0.01260%, ferric oxide yellow: 0.11490%, titanium dioxide: 0.25830%, iron oxide black: 0.03170%;
- the second layer: polyoxymethylene resin: 99.6660%, sunset red: 0.01008%, ferric oxide yellow: 0.09192%, titanium dioxide: 0.20664%, iron oxide black: 0.02536%;
- the third layer: polyoxymethylene resin: 99.7495%, sunset red: 0.00756%, ferric oxide yellow: 0.06894%, titanium dioxide: 0.15498%, iron oxide black: 0.01902%;
- the fourth layer: polyoxymethylene resin: 99.8330%, sunset red: 0.00504%, ferric oxide yellow: 0.04596%, titanium dioxide: 0.10332%, iron oxide black: 0.01268%;
- the fifth layer: polyoxymethylene resin: 99.9165%, sunset red: 0.00252%, ferric oxide yellow: 0.02298%, titanium dioxide: 0.05166%, iron oxide black: 0.00634%.
- In the method, the polyoxymethylene resin had a particle size of 60 µm and a molecular mass of 550000.
- This example differs from Example 1 in that the particle size of poly(methyl methacrylate) was 0.05 µm, and the others were the same as those of Example 1.
- This example differs from Example 1 in that the particle size of poly(methyl methacrylate) was 300 µm, and the others were the same as those of Example 1.
- This example differs from Example 1 in that the molecular mass of poly(methyl methacrylate) was 50000, and the others were the same as those of Example 1.
- This example differs from Example 1 in that the molecular mass of poly(methyl methacrylate) was 1500000, and the others were the same as those of Example 1.
- This example differs from Example 1 in that the resin powder is a polyether ether ketone powder, and the others were the same as those of Example 1.
- In this comparative example, the color transition change range between two adjacent layers was 0.05%, and the others were the same as those of Example 1. The specific composition of each layer was as follows:
- the first layer: poly(methyl methacrylate): 99.9354%, iron oxide red: 0.00131%, tartrazine: 0.01414%, titanium dioxide: 0.04687%, cobalt oxide: 0.00232%;
- the second layer: poly(methyl methacrylate): 99.9354%, iron oxide red: 0.00131%, tartrazine: 0.01413%, titanium dioxide: 0.04685%, cobalt oxide: 0.00232%;
- the third layer: poly(methyl methacrylate): 99.9354%, iron oxide red: 0.00131%, tartrazine: 0.01413%, titanium dioxide: 0.04682%, cobalt oxide: 0.00232%;
- the fourth layer: poly(methyl methacrylate): 99.9355%, iron oxide red: 0.00131%, tartrazine: 0.01412%, titanium dioxide: 0.04680%, cobalt oxide: 0.00232%;
- the fifth layer: poly(methyl methacrylate): 99.9355%, iron oxide red: 0.00131%, tartrazine: 0.01411%, titanium dioxide: 0.04678%, cobalt oxide: 0.00232%;
- the sixth layer: poly(methyl methacrylate): 99.9355%, iron oxide red: 0.00131%, tartrazine: 0.01410%, titanium dioxide: 0.04675%, cobalt oxide: 0.00231%;
- the seventh layer: poly(methyl methacrylate): 99.9356%, iron oxide red: 0.00131%, tartrazine: 0.01410%, titanium dioxide: 0.04673%, cobalt oxide: 0.00231%;
- the eighth layer: poly(methyl methacrylate): 99.9356%, iron oxide red: 0.00131%, tartrazine: 0.01409%, titanium dioxide: 0.04671%, cobalt oxide: 0.00231%;
- the ninth layer: poly(methyl methacrylate): 99.9356%, iron oxide red: 0.00130%, tartrazine: 0.01408%, titanium dioxide: 0.04668%, cobalt oxide: 0.00231%;
- the tenth layer: poly(methyl methacrylate): 99.9357%, red iron oxide: 0.00130%, tartrazine: 0.01408%, titanium dioxide: 0.04666%, cobalt oxide: 0.00231%;
- the eleventh layer: poly(methyl methacrylate): 99.9357%, red iron oxide: 0.00130%, tartrazine: 0.01407%, titanium dioxide: 0.04664%, cobalt oxide: 0.00231%;
- the twelfth layer: poly(methyl methacrylate): 99.9357%, iron oxide red: 0.00130%, tartrazine: 0.01406%, titanium dioxide: 0.04661%, cobalt oxide: 0.00231%;
- the thirteenth layer: poly(methyl methacrylate): 99.9357%, iron oxide red: 0.00130%, tartrazine: 0.01406%, titanium dioxide: 0.04659%, cobalt oxide: 0.00231%;
- the fourteenth layer: poly(methyl methacrylate): 99.9358%, iron oxide red: 0.00130%, tartrazine: 0.01405%, titanium dioxide: 0.04657%, cobalt oxide: 0.00230%;
- the fifteenth layer: poly(methyl methacrylate): 99.9358%, iron oxide red: 0.00130%, tartrazine: 0.01404%, titanium dioxide: 0.04654%, cobalt oxide: 0.00230%;
- the sixteenth layer: poly(methyl methacrylate): 99.9358%, red iron oxide: 0.00130%, tartrazine: 0.01403%, titanium dioxide: 0.04652%, cobalt oxide: 0.00230%;
- the seventeenth layer: poly(methyl methacrylate): 99.9359%, red iron oxide: 0.00130%, tartrazine: 0.01403%, titanium dioxide: 0.04650%, cobalt oxide: 0.00230%.
- In this comparative example, the color transition change range between two adjacent layers was 25%, and the others were the same as those of Example 1. The specific composition of each layer is as follows:
- the first layer: poly(methyl methacrylate): 99.9354%, iron oxide red: 0.00131%, tartrazine: 0.01414%, titanium dioxide: 0.04687%, cobalt oxide: 0.00232%;
- the second layer: poly(methyl methacrylate): 99.9515%, iron oxide red: 0.00098%, tartrazine: 0.01061%, titanium dioxide: 0.03513%, cobalt oxide: 0.00174%;
- the third layer: poly(methyl methacrylate): 99.9677%, iron oxide red: 0.00066%, tartrazine: 0.00707%, titanium dioxide: 0.02344%, cobalt oxide: 0.00116%;
- the fourth layer: poly(methyl methacrylate): 99.9838%, iron oxide red: 0.00033%, tartrazine: 0.00354%, titanium dioxide: 0.01172%, cobalt oxide: 0.00058%.
- This comparative example differs from Example 1 in that the mass percentage of the resin powder was 90%, and the mass percentage of the pigment was 10%, and the specific composition is as follows:
- the first layer: poly(methyl methacrylate): 83.3700%, iron oxide red: 0.33703%, tartrazine: 3.63781%, titanium dioxide: 12.05829%, cobalt oxide: 0.59687%;
- the second layer: poly(methyl methacrylate): 84.2015%, iron oxide red: 0.33703%, tartrazine: 3.45592%, titanium dioxide: 11.45538%, cobalt oxide: 0.56703%;
- the third layer: poly(methyl methacrylate): 85.0330%, iron oxide red: 0.30332%, tartrazine: 3.27403%, titanium dioxide: 10.85246%, cobalt oxide: 0.53718%;
- the fourth layer: poly(methyl methacrylate): 85.8645%, iron oxide red: 0.28647%, tartrazine: 3.09214%, titanium dioxide: 10.24995%, cobalt oxide: 0.50734%;
- the fifth layer: poly(methyl methacrylate): 86.6960%, iron oxide red: 0.26962%, tartrazine: 2.91025%, titanium dioxide: 9.64663%, cobalt oxide: 0.47750%;
- the sixth layer: poly(methyl methacrylate): 87.5275%, iron oxide red: 0.25277%, tartrazine: 2.72836%, titanium dioxide: 9.04372%, cobalt oxide: 0.44765%;
- the seventh layer: poly(methyl methacrylate): 88.3590%, iron oxide red: 0.23592%, tartrazine: 2.54647%, titanium dioxide: 8.44081%, cobalt oxide: 0.41781%;
- the eighth layer: poly(methyl methacrylate): 89.1905%, iron oxide red: 0.21907%, tartrazine: 2.36458%, titanium dioxide: 7.83789%, cobalt oxide: 0.38796%;
- the ninth layer: poly(methyl methacrylate): 90.0220%, iron oxide red: 0.20222%, tartrazine: 2.18269%, titanium dioxide: 7.23498%, cobalt oxide: 0.35812%;
- the tenth layer: poly(methyl methacrylate): 90.8535%, iron oxide red: 0.18536%, tartrazine: 2.00080%, titanium dioxide: 6.63206%, cobalt oxide: 0.32828%;
- the eleventh layer: poly(methyl methacrylate): 91.6850%, iron oxide red: 0.16851%, tartrazine: 1.81891%, titanium dioxide: 6.02915%, cobalt oxide: 0.29843%;
- the twelfth layer: poly(methyl methacrylate): 92.5165%, iron oxide red: 0.15166%, tartrazine: 1.63702%, titanium dioxide: 5.42623%, cobalt oxide: 0.26859%;
- the thirteenth layer: poly(methyl methacrylate): 93.3480%, iron oxide red: 0.13481%, tartrazine: 1.45513%, titanium dioxide: 4.82332%, cobalt oxide: 0.23875%;
- the fourteenth layer: poly(methyl methacrylate): 94.1795%, iron oxide red: 0.11796%, tartrazine: 1.27323%, titanium dioxide: 4.22040%, cobalt oxide: 0.20890%;
- the fifteenth layer: poly(methyl methacrylate): 95.0110%, iron oxide red: 0.10111%, tartrazine: 1.09134%, titanium dioxide: 3.61749%, cobalt oxide: 0.17906%;
- the sixteenth layer: poly(methyl methacrylate): 95.8425%, iron oxide red: 0.08426%, tartrazine: 0.90945%, titanium dioxide: 3.01457%, cobalt oxide: 0.14922%;
- the seventeenth layer: poly(methyl methacrylate): 96.6740%, iron oxide red: 0.06741%, tartrazine: 0.72756%, titanium dioxide: 2.41166%, cobalt oxide: 0.11937%.
- This comparative example differs from Example 1 in that the mass percentage of the resin powder was 99.9994%, and the mass percentage of the pigment was 0.0006%, and the specific composition is as follows:
- the first layer: poly(methyl methacrylate): 99.9990%, red iron oxide: 0.00002%, tartrazine: 0.00022%, titanium dioxide: 0.00073%, cobalt oxide: 0.00004%;
- the second layer: poly(methyl methacrylate): 99.9991%, red iron oxide: 0.00002%, tartrazine: 0.00021%, titanium dioxide: 0.00069%, cobalt oxide: 0.00003%;
- the third layer: poly(methyl methacrylate): 99.9991%, red iron oxide: 0.00002%, tartrazine: 0.00020%, titanium dioxide: 0.00065%, cobalt oxide: 0.00003%;
- the fourth layer: poly(methyl methacrylate): 99.9992%, red iron oxide: 0.00002%, tartrazine: 0.00019%, titanium dioxide: 0.00062%, cobalt oxide: 0.00003%;
- the fifth layer: poly(methyl methacrylate): 99.9992%, iron oxide red: 0.00002%, tartrazine: 0.00018%, titanium dioxide: 0.00058%, cobalt oxide: 0.00003%;
- the sixth layer: poly(methyl methacrylate): 99.9993%, red iron oxide: 0.00002%, tartrazine: 0.00016%, titanium dioxide: 0.00054%, cobalt oxide: 0.00003%;
- the seventh layer: poly(methyl methacrylate): 99.9993%, red iron oxide: 0.00001%, tartrazine: 0.00015%, titanium dioxide: 0.00051%, cobalt oxide: 0.00003%;
- the eighth layer: poly(methyl methacrylate): 99.9994%, red iron oxide: 0.00001%, tartrazine: 0.00014%, titanium dioxide: 0.00047%, cobalt oxide: 0.00002%;
- the ninth layer: poly(methyl methacrylate): 99.9994%, red iron oxide: 0.00001%, tartrazine: 0.00013%, titanium dioxide: 0.00044%, cobalt oxide: 0.00002%;
- the tenth layer: poly(methyl methacrylate): 99.9995%, red iron oxide: 0.00001%, tartrazine: 0.00012%, titanium dioxide: 0.00040%, cobalt oxide: 0.00002%;
- the eleventh layer: poly(methyl methacrylate): 99.9995%, red iron oxide: 0.00001%, tartrazine: 0.00011%, titanium dioxide: 0.00036%, cobalt oxide: 0.00002%;
- the twelfth layer: poly(methyl methacrylate): 99.9996%, red iron oxide: 0.00001%, tartrazine: 0.00010%, titanium dioxide: 0.00033%, cobalt oxide: 0.00002%;
- the thirteenth layer: poly(methyl methacrylate): 99.9996%, red iron oxide: 0.00001%, tartrazine: 0.0009%, titanium dioxide: 0.00029%, cobalt oxide: 0.00001%;
- the fourteenth layer: poly(methyl methacrylate): 99.9997%, red iron oxide: 0.00001%, tartrazine: 0.00008%, titanium dioxide: 0.00025%, cobalt oxide: 0.00001%;
- the fifteenth layer: poly(methyl methacrylate): 99.9997%, red iron oxide: 0.00001%, tartrazine: 0.00007%, titanium dioxide: 0.00022%, cobalt oxide: 0.00001%;
- the sixteenth layer: poly(methyl methacrylate): 99.9998%, red iron oxide: 0.00001%, tartrazine: 0.00005%, titanium dioxide: 0.00018%, cobalt oxide: 0.00001%;
- the seventeenth layer: poly(methyl methacrylate): 99.9998%, red iron oxide: 0.00000%, tartrazine: 0.00004%, titanium dioxide: 0.00015%, cobalt oxide: 0.00001%.
- the performance of the gradient resin obtained in Examples 1-8 and Comparative Examples 1-4 was tested, and the experimental results are shown in Table 1.
- In the test, the test standard of luminous transmittance refers to GB2410-2008, and the test method is as follows: a sample with a size of 30 mm × 30 mm × 1 mm was prepared, and tested by a haze meter.
- The test standard of flexural strength refers to ISO 10477-2018, and the test method is as follows:
Three-point flexural test: 5 strength bars of (2±0.1 mm) × (2±0.1 mm) × (25±1 mm) were cut for the flexural strength test. The inspector put the strength bar on an electric tensile testing apparatus for testing, and the spacing was 20 mm; the load was applied at a loading rate of 1±0.1 mm/min until the sample fractured; the 5 samples were tested respectively, and the strength value of each sample was recorded, and taken the average value. - The test standard of Vickers hardness refers to GB/T4340.1-2009, and the test method is as follows:
Three-point test: the finished product piece was placed on a Vickers hardness tester for testing, and hardness values at three different positions were measured and taken the average value. - Water absorption value and solubility value refers to ISO 10477-2018, and the test method is as follows:
5 test round pieces with a size of ϕ15±1 mm∗(1.0±0.2) mm were prepared. 2000-grit sandpaper was used for water polishing, and a caliper was used to measure the diameter and thickness of the samples to an accuracy of 0.01 mm. The sample volume was calculated and expressed in mm3. - 1) The samples were placed in a desiccator and dried in an oven at 37°C. After 22 h, the samples were placed in another desiccator at 23±2°C for 2 h. Then, one by one, the samples were taken out and weighed with a ten-thousandth balance to an accuracy of 0.1 mg. The above steps were continued until a constant weight was reached, which was denoted as m1;
- 2) The samples were taken out and stored in 20 mL water (constant-temperature water bath) at 37±1°C for 7 d, then taken out, washed with water, wiped for water on the surface and then tested, the samples were weighed with a ten-thousandth balance, and the mass was denoted as m2; and
- 3) The samples were placed into an oven at 37°C for 14-21 d until the weight kept constant, and then weighed with a ten-thousandth balance, and the mass was denoted as m3.
-
- In formula (1):
- m2 - the mass of the sample after being soaked in water for 7d with a unit of micrograms (µg);
- m3 - the constant mass of the sample after being soaked in water for 7d with a unit of micrograms (µg);
- V - the sample volume with a unit of cubic millimeters (mm3).
- The solubility value ρsl of 5 samples are calculated separately according to formula (2) with a unit of µg/mm3 to an accuracy of 0.1 µg/mm3:
m1 - the constant mass of the sample before being soaked in water with a unit of micrograms (µg);
m3 - the constant mass of the sample after being soaked in water for 7d with a unit of micrograms (µg);
V - the sample volume with a unit of cubic millimeters (mm3).Table 1 Luminous Transmittance (%) Flexural strength (MPa) Vickers Hardness (HV) Water Absorption Value (µg/cm3) Solubility value (µg/cm3) Example 1 62.6 110.7 24.5 20.3 1.2 Example 2 63.2 114.6 22.3 21.6 1.0 Example 3 58.9 136.2 25.7 18.3 0.7 Example 4 56.3 112.6 24.3 20.6 1.3 Example 5 63.2 111.9 23.9 19.9 1.1 Example 6 63.1 90.4 18.3 24.2 8.5 Example 7 / / / / / Example 8 / / / / / Comparative Example 1 62.5 110.7 24.5 20.3 1.2 Comparative Example 2 62.6 110.2 24.3 20.1 1.1 Comparative Example 3 62.4 110.6 24.5 20.3 1.2 Comparative Example 4 64.7 110.5 24.4 20.2 1.3 - As can be seen from Table 1, the gradient resin product obtained in the present application has no layer stratification; the color transition is natural, the layers merge into each other, no transition boundary can be found between layers, the interlayer color transition change range is 0.1%-20%, and it is invisible to the naked eye; the prepared gradient resin has a luminous transmittance of 55-65%, a flexural strength of more than 100 MPa, a Vickers hardness of more than 20 HV, a water absorption value of less than 25 µg/cm3, and a solubility value of less than 5 µg/cm3.
- The particle size of poly(methyl methacrylate) is too small in Example 4, which will cause cracks during pressing.
- The particle size of poly(methyl methacrylate) is too large in Example 5, resulting in that the pigment will be prevented from entering the powder inside, and the prepared disc will have non-uniform color.
- The molecular mass of poly(methyl methacrylate) is too small in Example 6, resulting in that the overall molecular mass of the product obtained from press molding will be too low, and the polymer with low molecular mass will be too much, which can be easily dissolved in the mouth.
- The molecular mass of poly(methyl methacrylate) is too large in Example 7, resulting in that the raw material cannot be melted and press-molded due to the excessively high hardness.
- The resin powder is replaced with polyether ether ketone in Example 8, resulting in that the melting and pressing cannot be achieved with the same process.
- The color transition change range between two adjacent layers is too small in Comparative Example 1, resulting in that the incisal of the tooth will have a dark color, and the incisal-edge effect of light incisal-edge color cannot be obtained.
- The color transition change range between two adjacent layers is too large in Comparative Example 2, resulting in that the color will show stratification and cannot transition naturally.
- The mass percentage of the resin powder is too small in Comparative Example 3, resulting in that the pigment content will be too high, the color will be too dark, and the tooth color consistent with the color guide cannot be customized.
- The mass percentage of the resin powder is too large in Comparative Example 4, resulting in that the pigment content will be low, the color will be too light, and the tooth color consistent with the color guide cannot be customized.
- Although the detailed process equipment and process flow of the present application are described through the above embodiments, the present application is not limited to the above detailed process equipment and process flow, which means that the present application is not necessarily rely on the above detailed process equipment and process flow to be implemented.
- Although the optional embodiments of the present application are described in detail herein, the present application is not limited to the specific details of the above embodiments.
- In addition, it should be noted that the specific technical features described in the above specific embodiments can be combined in any suitable manner unless they are inconsistent. The combination method will not be specified otherwise to avoid repetition.
Claims (12)
- A gradient resin, which is formed by merging different layers with color transition change, wherein the color transition change range between the two adjacent layers is 0.1-20%, and by mass percentage, the gradient resin is composed of 98-99.99% of a resin powder and 0.01-2% of a pigment.
- The gradient resin according to claim 1, wherein a particle size of the resin powder is 0.1-200 µm.
- The gradient resin according to claim 1 or 2, wherein a molecular mass of the resin powder is 100000-1000000.
- The gradient resin according to claim 3, wherein the molecular mass of the resin powder is 300000-700000, optionally 400000-600000.
- The gradient resin according to any one of claims 1 to 4, wherein a molecular mass of the resin powder is 30-150 µm, optionally 40-100 µm.
- The gradient resin according to any one of claims 1 to 5, wherein the resin powder comprises any one or a mixture of at least two of poly(methyl methacrylate), poly(ethyl methacrylate), poly(propyl methacrylate), poly(n-butyl methacrylate), poly(isobutyl methacrylate), poly(hexyl methacrylate), poly(dicyclopentenyl methacrylate), poly(tetrahydrofurfuryl methacrylate), poly(2-hydroxyethyl methacrylate), poly(glycidyl methacrylate), poly(lauryl methacrylate), poly(cyclohexyl methacrylate), poly(benzyl methacrylate), poly(allyl methacrylate), poly(2-ethoxyethyl methacrylate), methoxy polyethylene glycol methacrylate, poly(glycerol methacrylate), poly(isobornyl methacrylate), polyvinyl chloride, polystyrene, polyoxymethylene, polyacetaldehyde and polyurethane.
- The gradient resin according to any one of claims 1 to 6, wherein the pigment comprises any one or a mixture of at least two of zirconium vanadium yellow, cerium praseodymium yellow, tartrazine, ferric oxide yellow, chrome yellow, sunset red, iron oxide red, erbium oxide, titanium dioxide, cobalt oxide, chromium oxide, iron oxide brown, iron oxide black and carbon black.
- A preparation method for the gradient resin according to any one of claims 1 to 7, comprising:1) preparing colored powders: weighing and uniformly mixing the pigment and the resin powder for preparing colored powders with different colors according to respective color formulas, and weighing and proportioning the colored powders for each layer according to a layer configuration;2) spreading the materials: adding the colored powders with different colors obtained in step 1) into a molding mold in sequence, spreading one colored powder flat out in the molding mold, then adding another colored powder of the next layer and spreading the colored powder flat out until all the colored powders have been added; and3) performing a press molding: subjecting the mold to a hot-press molding, and taking the mold out after cooling, so as to obtain the gradient resin.
- The preparation method according to claim 8, wherein, in step 2), the color transition change range between two adjacent layers is 0.1-20%;optionally, in step 3), a temperature of the hot-press molding is 60-220°C, optionally 100-180°C, and more optionally 120-160°C;optionally, in step 3), a pressure of the hot-press molding is 1-20 MPa, optionally 4-15 MPa, and more optionally 8-12 MPa.
- The preparation method according to claim 8 or 9, wherein the preparation method further comprises a pretreatment step for the resin powder before step 1);
optionally, the pretreatment comprises drying, a temperature of the drying is 80-100°C, and a time of the drying is 1-3 h. - The preparation method according to any one of claims 8 to 10, comprising:1) preparing colored powders: drying the resin powder at 80-100°C for 1-3 h, weighing and uniformly mixing the pigment and the resin powder for preparing colored powders with different colors according to respective color formulas, and weighing and proportioning the colored powders for each layer according to a layer configuration;2) spreading the materials: adding the colored powders with different colors obtained in step 1) into a molding mold in sequence, spreading one colored powder flat out in the molding mold, then adding another colored powder of the next layer and spreading the colored powder flat out until all the colored powders have been added, wherein the color transition change range between two adjacent layers is 0.1-20%; and3) performing a press molding: subjecting the materials to be molded to a press molding in the mold, and removing the mold after molding, so as to obtain the gradient resin with natural interlayer transition and no color stratification, wherein an optional press method is a hot-press molding, and the mold is removed after cooling, a temperature of the hot-press molding is 60-220°C, and a pressure of the hot-press molding is 1-20 MPa.
- Use of the gradient resin according to any one of claims 1 to 7, wherein the gradient resin is used in preparing a gradient dental restoration.
Applications Claiming Priority (2)
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CN202011065904.4A CN112206170B (en) | 2020-09-30 | 2020-09-30 | Gradient resin and preparation method and application thereof |
PCT/CN2020/123042 WO2022067909A1 (en) | 2020-09-30 | 2020-10-23 | Gradient resin, preparation method therefor and use thereof |
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EP4129265A1 true EP4129265A1 (en) | 2023-02-08 |
EP4129265A4 EP4129265A4 (en) | 2024-04-17 |
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US (1) | US20230181428A1 (en) |
EP (1) | EP4129265A4 (en) |
CN (1) | CN112206170B (en) |
WO (1) | WO2022067909A1 (en) |
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CN113730264B (en) * | 2021-09-01 | 2024-03-12 | 爱迪特(秦皇岛)科技股份有限公司 | Dental gradient color resin ceramic restoration material and preparation method thereof |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
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GB514830A (en) * | 1937-05-12 | 1939-11-20 | Reichsverband Deutscher Dentis | Artificial denture parts and process for their manufacture |
US2454847A (en) * | 1944-04-29 | 1948-11-30 | H D Justi & Son Inc | Mold, mold charging, and molding process |
GB638981A (en) * | 1946-10-04 | 1950-06-21 | Raymond Mather | Improvements in or relating to the production of thermo-plastic mouldings such as artificial teeth |
JPH1085237A (en) * | 1996-09-12 | 1998-04-07 | Kenkichi Tei | Artificial tooth with gum and denture using it |
JPH10323353A (en) * | 1997-05-26 | 1998-12-08 | G C:Kk | Dental resin material and method for producing the same |
CN103273713B (en) * | 2013-06-13 | 2015-12-09 | 山东沪鸽口腔材料股份有限公司 | Four layers of look synthetic resin block and preparation method thereof |
CN105362084B (en) * | 2015-11-12 | 2019-04-19 | 深圳爱尔创口腔技术有限公司 | A kind of dental multi-layer-colored composite material and preparation method |
CN109589270B (en) * | 2017-09-30 | 2020-10-20 | 辽宁爱尔创生物材料有限公司 | Preparation method of dental material with gradually changed light transmittance and color and product prepared by preparation method |
CN108078789B (en) * | 2017-12-19 | 2020-12-18 | 上海沪亮生物医药科技有限公司 | Preparation method of multicolor integrated dental repair material |
CN108578251B (en) * | 2018-05-17 | 2021-06-25 | 上海沪亮生物医药科技有限公司 | Multicolor integrated dental repair material and preparation method thereof |
-
2020
- 2020-09-30 CN CN202011065904.4A patent/CN112206170B/en active Active
- 2020-10-23 US US17/925,764 patent/US20230181428A1/en active Pending
- 2020-10-23 EP EP20955929.3A patent/EP4129265A4/en active Pending
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US20230181428A1 (en) | 2023-06-15 |
WO2022067909A1 (en) | 2022-04-07 |
CN112206170A (en) | 2021-01-12 |
EP4129265A4 (en) | 2024-04-17 |
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